Transparent substrates comprising three-dimensional porous conductive graphene films and methods for making the same

Patent metadata

Field	Value
Publication number	US-11548811-B2
Application number	US-202117359739-A
Country	US
Kind code	B2
Filing date	Jun 28, 2021
Priority date	Mar 21, 2016
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

Abstract

Disclosed herein are graphene coatings characterized by a porous, three-dimensional, spherical structure having a hollow core, along with methods for forming such graphene coatings on glasses, glass-ceramics, ceramics, and crystalline materials. Such coatings can be further coated with organic or inorganic layers and are useful in chemical and electronic applications.

First claim

What is claimed is:

1. An article comprising:
a dense substrate having a surface roughness (RA) of 2 nm or less, the dense substrate comprising:
a glass, a glass ceramic, a ceramic, an inorganic crystalline or polycrystalline material; and
a porous coating layer having a thickness from about 100 nm to about 800 μm adhered to the substrate, the coating layer comprising:
a porous, three-dimensional construction having an average surface area from about 200 m 2 /g to about 2200 m 2 /g, the porous, three-dimensional construction comprising a network of a plurality of non-uniformly arranged three-dimensional graphene structures in contact with each other, and each of the three-dimensional graphene structures having a hollow core, wherein the three-dimensional graphene structure comprises five or less layers of graphene.

2. The article of claim 1 , wherein the hollow core of the three-dimensional graphene structure is substantially free of a metal or metal oxide.

3. The article of claim 1 , wherein an average diameter as measured by scanning electron microscope of the three-dimensional graphene structure is from about 50 nm to about 500 nm.

4. The article of claim 1 , wherein the average surface area of the porous, three-dimensional construction is from about 500 to 1500 m 2 /g.

5. The article of claim 1 , wherein the porous, three-dimensional construction has a porosity of from about 90% to about 99.6% as measured by scanning electron microscope.

6. The article of claim 1 , wherein the adhesion of the coating layer to the substrate exhibits an effective adhesion energy at the interface of the coating layer and the substrate of from about 0.1 J/m 2 to about 4 J/m 2 , and the substrate is a transparent substrate.

7. The article of claim 1 , wherein the substrate comprises a transparent material and the optical transmission of the article, as measured by ultraviolet-visible spectroscopy, is greater than 60% at 550 nm.

8. A device comprising the article of claim 1 .

9. A method of forming the article of claim 1 , the method comprising:
(a) depositing a metal from a source onto a surface of a dense substrate to form a metallic layer comprising metal particles wherein the dense substrate has a surface roughness (RA) of 2 nm or less, the dense substrate comprising: a glass, a glass ceramic, a ceramic, an inorganic crystalline or polycrystalline material;
(b) depositing, via chemical vapor deposition of a carbon-source gas with an optional hydrogen-gas source, an optionally substituted graphene layer on the metallic layer to form a porous coating layer having a thickness from about 100 nm to about 800 μm adhered to the substrate, the coating layer comprising a porous, three-dimensional construction having an average surface area from about 200 m 2 /g to about 2200 m 2 /g, and
(c) removing the metallic layer by thermal or chemical processes to create an optionally substituted, three-dimensional hollow graphene structure such that the porous, three-dimensional construction comprises a network of a plurality of non-uniformly arranged three-dimensional graphene structures in contact with each other and each of the three-dimensional graphene structures having a hollow core, wherein the three-dimensional graphene structure comprises five or less layers of graphene.

10. The method of claim 9 , wherein steps (b) and (c) occur simultaneously or partially overlap.

11. The method of claim 10 , wherein the metal comprises a transition metal, and the chemical vapour deposition occurs at a temperature from about 200° C. to about 800° C.

12. The method of claim 9 , wherein the metal particles comprise copper, cobalt, nickel, iron, zinc, silver, or gold particles.

13. The method of claim 12 , wherein the metal particles are nanoparticles having a diameter along their longest axis from about 5 nm to about 500 nm.

14. The method of claim 9 , wherein the carbon-source gas is chosen from CH 4 , C 2 H 2 , CF 4 , CHF 3 , C 2 F 6 , C 2 H 6 , C 3 H 8 , C 3 H 6 , C 6 H 14 , C 6 H 6 , C 6 H 5 CH 3 , and combinations thereof.

15. The method of claim 14 , wherein the carbon-source gas has a pressure of from about 1×10 −4 to 100 Torr and the chemical vapor deposition is done at a temperature greater than 600° C.

16. The method of claim 9 , where removing of the metallic layer is done by heating the graphene coated metallic layer to a temperature sufficient to vaporize the metallic layer.

17. The method of claim 9 , where removing of the metallic layer is done by soaking the graphene coated metallic layer in a chemical compound that dissolves or removes the metallic layer.

18. The method of claim 17 , wherein the chemical compound comprises ammonium persulfate, iron chloride, iron nitrate, copper chloride, hydrochloric acid, nitric acid, sulphuric acid, hydrogen peroxide, and combination thereof.

Assignees

• Corning Inc
• Icfo—The Inst Of Photonic Science
• Inst Catalana De Recerca I Estudis Avancats Icrea
• Icfo—The Inst Of Photonic Sciences

Inventors

• Li Connie
• Liu Xinyuan
• Martín-Francés Miriam Marchena
• Pruneri Valerio
• Senaratne Wageesha
• Song Zhen
• Soni Kamal Kishore

Classifications

• C03C2218/152

  by cvd · CPC title

• C03C2217/425

  consisting of a porous layer · CPC title

• C03C2218/33

  by etching · CPC title

• C01B32/186

  by chemical vapour deposition [CVD] · CPC title

• C01P2004/34

  hollow · CPC title